CN206219401U - A kind of biochemical treatment system of Texaco stove coal gas wastewater high efficient resourcing - Google Patents

Abstract

A kind of biochemical treatment system of Texaco stove coal gas wastewater high efficient resourcing, including Heisui River subsider, Ca²⁺Reaction settling basin, water leg, MAP reaction settling basins and biological treatment system, the top delivery port of the Heisui River subsider connect the import of the first draining pump, the outlet connection Ca of the first draining pump by valve on subsider²⁺The lower water inlet of reaction settling basin, Ca²⁺The top delivery port of reaction settling basin connects water leg by the second draining pump, and water leg connects MAP reaction settling basins by the 3rd draining pump, and MAP reaction settling basins connect the Anaerobic Treatment unit in biological treatment system by the 4th draining pump；The utility model can be realized to NH₄ ⁺‑N、Ca²⁺、Mg²⁺The target that ion is efficiently removed and recycled, while greatly reducing waste water hardness, improves the easy scale problems of water quality, equipment overhaul cycle is extended about more than 6 months, realizes the theory of recycling industries and clean production.

Description

A kind of biochemical treatment system of Texaco stove coal gas wastewater high efficient resourcing

Technical field

The utility model is related to industrial waste water treatment, and especially a kind of Texaco stove coal gas wastewater is efficiently provided The biochemical treatment system in source.

Background technology

Increasingly in short supply due to global range petroleum resources, China's Coal Chemical Industry turns into the strategy weight of economic development in recent years Point, particularly producing clear energy sources（Such as hydrogen, methane, methyl alcohol）Or substitute petrochemicals（Such as ethylene raw, poly- third Alkene raw material, dimethyl ether etc.）Based on New Coal Chemical the industry development impetus it is powerful.Wherein Texaco（GE）Coal water slurry gasification skill Art is one of more successful Coal Gasification Technology of current domestic and international application, has had the applicating history of more than 30 years, 2013 in China The oil plant such as Maoming, Zibo, Jiujiang, Nanjing, Anqing has built a series of extensive GE coals hydrogen manufacturing gasification installations after year.But coal gas All there is the environmental issue that water consumption is big, wastewater discharge is big, and waste water quality by coal raw material and different gasification works in chemical industry skill Skill decision, such as lignite, bituminous coal, anthracite, coke and different coal gasifying process：Fixed bed（Lurgi gasifier）, fluid bed（Winkler Stove）And air flow bed（Texaco stove）Deng waste water quality has very big difference.Therefore the treatment technology of research waste water not only can be real The recycling of existing waste water resource, saving water resource, and also it is significant for environmental protection.

Temperature, pressure process water higher, black, solid content 10- are expelled directly out from GE gasification furnaces, wash tower bottoms 15% and dissolved with H₂S、CO₂、NH₃It is referred to as Heisui River Deng gas；Heisui River enters subsider after multistage flash evaporation, at clarification of flocculating Water outlet after reason is buck, and its solid content is further reduced, H₂S、CO₂、NH₃Reduced Deng gas content.In order to reduce technique consumption Water, the buck for having nearly 3/4ths is back to use in gasification furnace again as chilled water, and the buck of remainder enters sewage disposal System.But due in buck except dissolubility high concentration NH₄ ⁺- N, also contains Ca²⁺1200-1400mg/L、Mg²⁺100-200mg/ L, the two is far above mixing saturated aqueous solution hardness 323.1mg/L (with CaCO₃Meter), so causing Quench water pipeline and water-supply-pipe Knot dirt is serious, every gasifier operation 30-50 days, inner-walls of duct fouling thickness about 2-5cm.Major Coal Chemical Industry enterprises in production process There is the experience for being forced all fronts parking maintenance due to pipeline serious scale in industry.In addition, waste water enters sewage disposal system Afterwards, high concentration NH₄ ⁺- N causes carbon-nitrogen ratio low, and is unfavorable for that subsequent biochemical is processed.Conventional biochemical process is A/O systems at present, There is biochemical system fluctuation of service in real process, sludge easily expands, total nitrogen concentration is exceeded, be difficult to remove, be drop total nitrogen Cause reflux ratio it is high, usually from 16:1, so power consumption phenomenon high.But existing coal gasification waste water treatment technology, such as China are specially Profit：201310220988.8th, 201010546162.7,201110030443.1,201020679280.0, etc., for Shandong Strange stove high concentrated organic wastewater, handling process is extremely complex, is unsuitable for Texaco gasifier quality problem.

Utility model content

The utility model aims to provide one kind and can realize to NH₄ ⁺-N、Ca²⁺、Mg²⁺Ion efficiently removal and recycling Target, while greatly reduce waste water hardness, improve the easy scale problems of water quality, equipment overhaul cycle is extended about 6 months More than, realize the biochemical treatment system of the Texaco stove coal gas wastewater high efficient resourcing of the theory of recycling industries and clean production System.

To achieve the above object, the utility model provides following technical scheme：A kind of Texaco stove coal gas wastewater is efficient The biochemical treatment system of resource, including Heisui River subsider, Ca²⁺Reaction settling basin, water leg, MAP reaction settling basins and biology Processing system, the top delivery port of the Heisui River subsider connects the import of the first draining pump, first by valve on subsider The outlet connection Ca of draining pump²⁺The lower water inlet of reaction settling basin, Ca²⁺The top delivery port of reaction settling basin passes through second Draining pump connects water leg, and water leg connects MAP reaction settling basins by the 3rd draining pump, and MAP reaction settling basins pass through the 4th Anaerobic Treatment unit in draining pump connection biological treatment system；Biological treatment system is by Anaerobic Treatment unit, Aerobic Process for Treatment list Unit and second pond composition, the wherein discharge outlet of Anaerobic Treatment unit connect aerobic treatment unit, aerobic place by the 5th draining pump The top discharge outlet for managing unit connects second pond by pipeline, and second pond top connects Anaerobic Treatment by sewage backflow pipe The water inlet of unit, second pond bottom connects Anaerobic Treatment unit and aerobic treatment unit by mud return line.

As further scheme of the present utility model：Subsider lower valve is installed at the bottom slag discharge of the Heisui River subsider Door.

As further scheme of the present utility model：The Ca²⁺The bottom of reaction settling basin is connected by a mud valve A number precipitation collecting pit, a precipitation collecting pit connects precipitation filter by filter feed pump.

As further scheme of the present utility model：The bottom of the MAP reaction settling basins is connected by No. two mud valves No. two precipitation collecting pits, No. two precipitation collecting pits connect MAP recovery device by feed pump.

As further scheme of the present utility model：The mud return line connects Aerobic Process for Treatment by a return valve Unit, Anaerobic Treatment unit is connected by No. two return valves, and mud return line connects the discharge of second pond by the pipe valve that flows back Pipeline；Sewage backflow pipe is provided with sewage backflow valve.

As further scheme of the present utility model：The Ca²⁺It is respectively equipped with reaction settling basin and MAP reaction settling basins A number agitator and No. two agitators.

As further scheme of the present utility model：The Ca²⁺Reaction settling basin top is set plus NaOH is managed and added Na₂CO₃Pipe, MAP reaction settling basins top sets and adds magnesium salts pipe, the salt pipe that phosphorates, adds NaOH pipes and a pH value detector；Anaerobism The water inlet of processing unit sets acid adding pipe, and top is provided with No. two pH detectors.

As further scheme of the present utility model：The Anaerobic Treatment unit inlet end pond it is long 1/5th at Core wall is set, Anaerobic Treatment unit is divided into two ponds, several baffle plates are being set in the pond of inlet end.

Compared with prior art, the beneficial effects of the utility model are：The Texaco stove coal gas wastewater high efficient resourcing Biochemical treatment system there is advantages below：First, NH in Texaco gasifier coal process for making hydrogen waste water₄ ⁺- N concentration is 280-400 Mg/L, COD are 800-1200 mg/L, and its hardness usually between 1200-1460mg/L, exceeded well over and mix both at 25 DEG C 323. 1mg of the hardness/L of saturated aqueous solution afterwards is (with CaCO₃Meter), therefore feed-line fouling is serious in production, opposite Produce influence very big.This patent is first to Ca²⁺After ion carries out precipitation process, further acted synergistically by MAP sedimentations, will Hardness is reduced to below 60-150mg/L, greatly reduces waste water hardness, improves the easy scale problems of water quality, makes overhaul of the equipments week Phase extends about more than 6 months.

2nd, because prevailing system waste water carbon-nitrogen ratio is low, cause that biochemical system NH_3-N treating is difficult up to standard and total nitrogen is exceeded Phenomenon is serious.By controlling MAP deposition conditions in this patent, make waste water NH₄ ⁺- N clearances are up to 60-90%, therefore significantly reduce The NH of subsequent biochemical processing system₄ ⁺- N loads, former carbon-nitrogen ratio 3:1 brings up to 8:More than 1, former A/O reflux ratios 16:1 is reduced to 0.5:1-2.0:1, total nitrogen emission reduction is improved more than 20-30%, greatly improve biochemical effects, it is ensured that NH₄ ⁺- N, TN qualified discharges and System stable operation, and energy consumption is significantly reduced, reduce cost for wastewater treatment.

3rd, this patent is to Ca²⁺、Mg²⁺Ion and NH₄ ⁺- N is precipitated respectively, and the precipitation of generation is with CaCO₃With ammonium magnesium phosphate MAP Based on, its CaO content is higher than 52%, MgNH₄PO₄·6H₂O content is higher than 97%, has obtained the construction material and high-quality of high-quality Industrial chemicals or agricultural slow-release fertilizer are reclaimed, therefore realize the theory of recycling industries and clean production.

Brief description of the drawings

Fig. 1 is structural representation of the present utility model.

Fig. 2 is the structural representation of Anaerobic Treatment unit of the present utility model.

Specific embodiment

Below in conjunction with the accompanying drawing in the utility model embodiment, the technical scheme in the utility model embodiment is carried out Clearly and completely describe, it is clear that described embodiment is only a part of embodiment of the utility model, rather than whole Embodiment.Based on the embodiment in the utility model, those of ordinary skill in the art are not under the premise of creative work is made The every other embodiment for being obtained, belongs to the scope of the utility model protection.

Fig. 1-2 is referred to, in the utility model embodiment, a kind of biochemistry of Texaco stove coal gas wastewater high efficient resourcing Processing system, including Heisui River subsider 1, Ca²⁺Reaction settling basin 2, water leg 3, MAP reaction settling basins 4 and biological treatment system, The top delivery port of the Heisui River subsider 1 connects the import of the first draining pump 10, the first draining pump by valve 9 on subsider 10 outlet connection Ca²⁺The lower water inlet of reaction settling basin 2, Ca²⁺The top delivery port of reaction settling basin 2 passes through second row Water pump 18 connects water leg 3, and water leg 3 connects MAP reaction settling basins 4 by the 3rd draining pump 19, and MAP reaction settling basins 4 lead to The Anaerobic Treatment unit 5 crossed in the connection biological treatment system of the 4th draining pump 29；Biological treatment system by Anaerobic Treatment unit 5, Aerobic treatment unit 6 and second pond 7 are constituted, and wherein the discharge outlet of Anaerobic Treatment unit 5 connects aerobic by the 5th draining pump 34 Processing unit 6, the top discharge outlet of aerobic treatment unit 6 connects second pond 7 by pipeline, and the top of second pond 7 is by dirt The water inlet of the connection Anaerobic Treatment of water return duct 35 unit 5, the bottom of second pond 7 connects Anaerobic Treatment list by mud return line 40 Unit 5 and aerobic treatment unit 6.

It is above-mentioned, subsider lower valve 8 is installed at the bottom slag discharge of Heisui River subsider 1.

It is above-mentioned, Ca²⁺The bottom of reaction settling basin 2 connects a precipitation collecting pit 15 by a mud valve 14, and No. one is sunk Shallow lake collecting pit 15 connects precipitation filter 17 by filter feed pump 16.

Above-mentioned, the bottom of MAP reaction settling basins 4 connects No. two precipitation collecting pits 26 by No. two mud valves 25, and No. two are sunk Shallow lake collecting pit 26 connects MAP recovery device 28 by feed pump 27.

Above-mentioned, mud return line 40 connects aerobic treatment unit 6 by a return valve 38, by No. two return valves 39 connection Anaerobic Treatment units 5, mud return line connects the discharge line of second pond 7 by the pipe valve 37 that flows back；Sewage backflow pipe 35 are provided with sewage backflow valve 36.

It is above-mentioned, Ca²⁺An agitator 11 and No. two agitators are respectively equipped with reaction settling basin 2 and MAP reaction settling basins 4 20。

It is above-mentioned, Ca²⁺The top of reaction settling basin 2 is set plus NaOH pipes 12 and plus Na₂CO₃Pipe 13, MAP reaction settling basins 4 are pushed up Portion sets and adds magnesium salts pipe 21, the salt pipe 22 that phosphorates, adds NaOH pipes 23 and a pH value detector 24.

It is above-mentioned, in the water inlet of Anaerobic Treatment unit 5, acid adding pipe 32 is set, top is provided with No. two pH detectors 33.

It is above-mentioned, Anaerobic Treatment unit 5 inlet end pond it is long 1/5th at set core wall 30, by Anaerobic Treatment list Unit 5 is divided into two ponds, and several baffle plates 31 are being set in the pond of inlet end.

Ammonium magnesium phosphate（MAP）The precipitation method are at present to dissolution of contaminated water NH₄ ⁺A kind of-N removals method the most rapidly and efficiently, With making waste water nitrogen phosphor resource technical advantage.Its action principle is：There is Mg in sewage or solution²⁺、PO₄ ^3–、NH₄ ⁺Three kinds of ions In the presence of, and ion concentration product is more than MgNH₄PO₄·6H₂During O solubility product constants, there is MgNH₄PO₄·6H₂O is produced, equation For：Mg²⁺+PO₄ ^3–+NH₄ ⁺+6H₂O↔MgNH₄PO₄·6H₂O↓。MgNH₄PO₄·6H₂O is white, and it is guanite to be commonly called as（MAP）, it is A kind of industrial chemicals or agriculture slow release fertilizer.NH in the waste water that Texaco's coal process for making hydrogen is produced₄ ⁺- N concentration is usually in 280- 400mg/L, belongs to middle low concentration, therefore the method removing such as not easy-to-use stripping, extraction, rectifying, and otherwise cost high benefit is low.And moral Scholar's Gu furnace gas temperature, pressure is high, and harmful components are simpler in technique waste water, hardly oil-containing and aldehydes matter, COD contents compared with It is low, often in 800-1200mg/L, therefore the utility model MAP sedimentations reduction waste water NH₄ ⁺- N content, transforms existing water The circulatory system, and by Chinese patent " a kind of device that guanite resource recovery is carried out to waste water nitrogen phosphorus " （201420458242.0）Precipitation is reclaimed and is utilized as slow-release fertilizer.But contain high concentration Ca in waste water²⁺Ion, in pH value in reaction Just there is more than 30% Ca during more than 8.0, in water²⁺Ion conversion is Ca₅OH(PO4)₃(HAP).Coal process for making hydrogen produces wastewater flow rate Huge, per hour when the mark of output 200,000 cubic meter, the plant hydrogen that purity is more than 97.5%, 4.8 MPas, waste water yield is about It is 400 tons/h, because the big precipitation capacity for then producing daily of wastewater flow rate is also considerable.As removed Ca in advance²⁺Ion, you can obtain High-purity MgNH₄PO₄·6H₂O, is very valuable industrial chemicals.Therefore be combined together for two methods by this patent, sternly Lattice control operation condition, finally realizes to NH₄ ⁺-N、Ca²⁺、Mg²⁺The target that ion is efficiently removed and recycled, while greatly Ground reduces waste water hardness, improves the easy scale problems of water quality, equipment overhaul cycle is extended about more than 6 months, realizes circulation warp The theory of Ji and clean manufacturing.

Design feature of the present utility model and its principle：The top water outlet of Heisui River subsider 1 enters Ca²⁺Reaction settling basin 2, Inflow reaches Ca²⁺After a quarter of the volume of reaction settling basin 2, an agitator 11 is opened, it is 300- to control rotating speed 350rpm, opens plus NaOH pipes 12 are to dosing completion, while after keeping an agitator 11 to continue to stir 15-20min, opening and adding NaCO₃Pipe 13 to dosing is completed, and after continuing to stir 30min after the completion of water inlet and dosing all, adjustment agitator speed is 200- 250rpm, and continue stirring 15-20min after, stop an agitator 11 simultaneously stand.After a number agitator 11 stops, opening another One Ca²⁺Reaction settling basin, is equally operated, different Ca²⁺Reaction settling basin batch (-type) alternate run, according to what is produced The volume of water and reaction tank determines the Ca for needing²⁺Reaction settling basin quantity.Stop in an agitator 11 and stand 1.5-2h Afterwards, open and Ca²⁺The second connected draining pump 18 of the top discharge outlet of reaction settling basin 2, after the second draining pump 18 is precipitated Waste water is discharged into water leg 3.Work as Ca²⁺After reaction settling basin 2 racks up waste water, after opening bottom precipitation outlet valve 14, precipitation Into a precipitation collecting pit 15, precipitation filter 17 is entered by filter feed pump 16.Due to texaco gasification furnace temperature Height, coal gasification procedure decomposition is more complete, therefore by after the precipitation of Heisui River subsider 1, water quality is more as clear as crystal, and SS is only 20-60mg/L, so white is precipitated as, with CaCO₃It is main component, CaO content is higher than 52% after measured, can be used as fabulous Construction material is reclaimed, and in the precipitation filtering Hou Song brickmaking of filter 17, building materials raw material does in factory.

In above-mentioned, the bottom precipitation of Heisui River subsider 1 is that thick slag is arranged by the way that subsider lower valve 8 is outer.

In above-mentioned, in Ca²⁺The top of reaction settling basin 2 sets and adds NaOH pipes 12, adds Na₂CO₃In pipe 13, described NaOH is Chemistry is pure, analyze pure or industrial NaOH, is added after being configured to saturated solution or any concentration, the control of NaOH additions with it is useless Ca in water²⁺The mol ratio of ion is 0.3:1—0.5:1, described NaCO₃For chemistry is pure, analyze pure or industrial NaCO₃, can It is configured to saturated solution or any concentration or solid mode is added, Na₂CO₃Addition control with Ca in waste water²⁺Ion Mol ratio be 0.85:1--1.00:1.For dissolved solid NaOH, Na₂CO₃Aqueous solvent can be the downflow weir of second pond 7 Water outlet, can so save fresh water consumption in technique, while reducing wastewater emission amount.NaOH and Na₂CO₃With Ca in waste water²⁺、 With a small amount of Mg²⁺Ion fully reacts under agitation, generates CaCO₃、Ca(OH)₂、MgCO₃、Mg(OH)₂It is heavy etc. form Form sediment, considerably reduce the concentration of scale-forming ion in waste water.

In above-mentioned, the water outlet of the downflow weir of water leg 3 enters MAP reaction settling basins 4 by the 3rd draining pump 19.In inflow After reaching a quarter of the volume of MAP reaction tanks 4, No. two agitators 20 are opened, control rotating speed for 300-350rpm, opened plus magnesium Salt pipe 21 to dosing is completed, and after keeping No. two agitators 20 to continue to stir 10-15min, is opened salt pipe 22 to the dosing that phosphorates and is completed, And be kept stirring for, after the completion of water inlet and dosing all, by a pH value detector 24 and plus NaOH pipes 23, adjust reaction solution PH value is not less than 9.0, and after continuing to stir 10-15min after the completion of water inlet and dosing all, No. two rotating speeds of agitator 20 of adjustment are 150-200rpm, after stirring 20-30min, stops No. two agitators 20 and stands.After No. two agitators 20 stop, opening another Platform MAP reaction settling basins, are equally operated, different MAP reaction settling basin batch (-type) alternate runs, according to the water for producing Volume with reaction tank determines the MAP reaction settling basin quantity of needs.After No. two agitators 20 stop and stand 1.5-2h, open Open the 4th draining pump 29 being connected with the top discharge outlet of MAP reaction settling basins 4.

In above-mentioned, in the top of MAP reaction settling basins 4 sets and adds magnesium salts pipe 21, the salt pipe 22 that phosphorates, plus NaOH pipes 23, one Number pH value detector 24, described magnesium salts is for chemistry is pure, analyze pure or industrial MgCl₂、MgSO₄With the one kind in MgO, prepare Added by magnesium salts pipe 21 after into saturated solution or any concentration, it is 1.2 that addition is controlled in the mol ratio with addition microcosmic salt: 1--1.5:1；Described microcosmic salt is for chemistry is pure, analyze pure or industrial NaH₂PO₄、Na₂HPO₄、Na₃PO₄、KH₂PO₄、K₂HPO₄With H₃PO₄In one kind, added by microcosmic salt pipe 22 after being configured to saturated solution or any concentration, addition control in waste water NH₄ ⁺The mol ratio of-N is 0.6:1--1.1:1.For dissolve magnesium salts, microcosmic salt, NaOH aqueous solvent can be the downflow weir of second pond 7 Water outlet, can so save fresh water consumption in technique, at the same reduce wastewater emission amount.Pass through a pH after the completion of dispensing The value detection reacting solution pH value of detector 24, NaOH solution is added by adding NaOH pipes 23, and regulation reacting solution pH value is not less than 9.0.The PO in waste water under stirring and alkalescence condition₄ ^3–And NH₄ ⁺、Mg²⁺Ion fully reacts, generation MAP precipitations, NH in waste water₄ ⁺- N clearances reach 60-90%, hardness and are reduced to 60-150mg/L, control in less scaling safe range.

In above-mentioned, waste water passes through the 4th draining pump 29 with returning from sewage backflow pipe 35 after MAP reaction settling basins 4 are precipitated The water inlet of anaerobic reaction unit 5 is discharged into after stream sewage mixing, the inlet flow-patterm of reduction Anaerobic Treatment unit 3 is diluted by recirculation water Value, the sour dosage needed for regulation water inlet pH value can be greatly decreased, makes the acid adding amount of Anaerobic Treatment unit 3 only need theoretical dosage 1/6-1/11.In the inlet end of anaerobic reaction unit 5 process that acid adding is adjusted is completed by 32, No. two pH detectors 33 of acid adding pipe Afterwards, rear pH value of waste water is sufficiently mixed by baffling section and reaches 8.5 or so the Anaerobic Treatment sections for entering anaerobic reaction unit 5, waterpower Residence time 3.5-4.5h.The discharge outlet water outlet of Anaerobic Treatment unit 5 enters aerobic treatment unit 6, and dissolved oxygen concentration is 2.5- 3.0mg/L, after Aerobic Process for Treatment 4-5h, water outlet enters second pond 7, and the water part of the downflow weir of second pond 7 is discharged, and a part passes through Sewage backflow pipe 35 is back to the water inlet of Anaerobic Treatment unit 5, and reflux ratio 0.5 is controlled by sewage backflow valve 36:1-2.0:1, Significantly reduce former A/O system flowbacks and compare 16:1, reducing energy consumption.The residual active sludge that sedimentation basin 7 is produced passes through sludge reflux Pipe 40 and the backflow return valve 39 of return valve 38, two of pipe valve 37, are controlled, and a part returns to Anaerobic Treatment unit 5, one Part returns to aerobic treatment unit 4, to supplement the sludge of loss, while the sludge discharge of biochemical system is greatly reduced.

In above-mentioned, after MAP reaction settling basins 4 rack up waste water, after opening bottom precipitation outlet valve 25, precipitation enters No. two precipitation collecting pits 26, MAP recovery device 28 is entered by filter feed pump 27.Described MAP recovery device 28 refers to Chinese patent " a kind of device that guanite resource recovery is carried out to waste water nitrogen phosphorus "（201420458242.0）.Due to have passed through The precipitation process of early stage, therefore the precipitation that MAP reaction settling basins 4 are produced is very pure, is white, by MAP recovery device 28 After dehydrating, ammonium magnesium phosphate content is higher than 97%, can be reclaimed as the industrial chemicals of high-quality or agricultural slow-release fertilizer, is realized The theory of recycling industries and clean production, while also reducing subsequent biochemical processing cost.

In above-mentioned, MAP reaction settling basins 4 are intermittent operation, according to actual aquifer yield and reactor volume in production, are matched somebody with somebody Put more than 2-4 platforms.

In above-mentioned, Anaerobic Treatment unit 5 inlet end about pond it is long 1/5th at set core wall 30, at anaerobism Reason unit 5 is divided into two ponds, and baffle plate 31 is set in the pond of inlet end, runs current baffling, plays and fully mixes water The effect of stream.

In above-mentioned, a part of water outlet of the downflow weir of second pond 7 is back to Anaerobic Treatment unit 5 and enters into sewage backflow pipe 35 At the mouth of a river, the water with MAP reaction precipitations 4 mixes, and this reflux type plays dilution and reduces the water inlet pH value of Anaerobic Treatment unit 5 Effect, can be greatly decreased regulation water inlet pH value needed for sour dosage, make the acid adding amount of Anaerobic Treatment unit 5 only need theory to add The 1/6-1/11 of amount.

Application examples one：

With the waste water that China Petroleum ＆ Chemical Co., Ltd. Maoming Branch's Texaco gasifier coal process for making hydrogen is produced It is objective for implementation, Ca is contained in the waste water after being precipitated through Heisui River subsider²⁺1150-1300mg/L、Mg²⁺120-150mg/L、NH₄ ⁺- N292.8-358.7mg/L, COD988.6-1023.2mg/L, SS are 26-40mg/L, pH value 8.1-8.34, on the subsider of Heisui River Portion's water outlet enters Ca²⁺Reaction settling basin, Ca is reached in inflow²⁺After a quarter of reaction settling basin volume, stirring is opened Device, controls rotating speed for 300-350rpm, opens plus NaOH pipes to dosing is completed, the control of NaOH additions with Ca in waste water²⁺From The mol ratio of son is 0.3:1-0.5:1, after being kept stirring for device stirring 15-20min, open plus Na₂CO₃Pipe to dosing is completed, Na₂CO₃Addition control with Ca in waste water²⁺The mol ratio of ion is 0.85:1--1.00:1.With going out for second pond downflow weir Water dissolves Na₂CO₃, NaOH, can so save fresh water consumption in technique, at the same reduce wastewater emission amount.In water inlet and dosing After the completion of all continue stir 30min after, adjustment agitator speed be 200-250rpm, and continue stirring 15-20min after, stopping Agitator simultaneously stands.After agitator stops and stands 1.5-2h, open and Ca²⁺The connected row of reaction settling basin top discharge outlet Water pump, water is discharged into water leg after draining pump is precipitated.Work as Ca²⁺After reaction settling basin racks up waste water, bottom precipitation is opened After outlet valve, precipitation enters precipitation collecting pit, and precipitation filter is entered by filter feed pump, in precipitation filter filtering Building materials raw material does in Hou Song brickmaking factory.

The water outlet of water leg downflow weir enters MAP reaction settling basins by draining pump, and MAP reaction pond bodies are reached in inflow After long-pending a quarter, turn on agitator controls rotating speed for 300-350rpm, opens plus magnesium salts pipe to dosing is completed, addition It is 1.2 to control in the mol ratio with addition microcosmic salt:1--1.5:1, after being kept stirring for device continuation stirring 10-15min, opening phosphorates Salt pipe to dosing complete, addition control with NH in waste water₄ ⁺The mol ratio of-N is 0.6:1—1.1:1, and be kept stirring for, Water inlet and dosing all after the completion of, by pH value detector and plus NaOH manage, regulation reacting solution pH value be not less than 9.0.It is heavy with two Pond downflow weir goes out water dissolves magnesium salts, microcosmic salt, NaOH, can so save fresh water consumption in technique, while reducing discharge of wastewater Total amount.After continuing to stir 10-15min after the completion of water inlet and dosing all, adjustment agitator speed is 150-200rpm, stirring After 20-30min, stop agitator and stand.After 1.5-2h is stood, unlatching is connected with MAP reaction settling basins top discharge outlet Draining pump, the waste water after precipitation is entered by Anaerobic Treatment unit by draining pump.It is to effluent monitoring index now：NH₄ ⁺- N31.3-80.4mg/L, hardness are 46.4-102.2mg/L, COD693.5-1080.7mg/L, pH value 8.92-9.99.When MAP is anti- After answering sedimentation basin to rack up waste water, bottom precipitation outlet valve is opened, precipitation enters precipitation collecting pit, by filter feed pump Into MAP recovery device.

Waste water after precipitation mixes when entering Anaerobic Treatment unit with the recirculation water from second pond, and pH value of waste water significantly drops It is low, pH8.12-8.94 is generally lowered into, the sour dosage needed for regulation water inlet pH value or need not be so greatly decreased.By adding Acid tube adds hydrochloric acid, and due to the effect of Anaerobic Treatment unit Internal baffle, hydrochloric acid is fully mixed with waste water, after regulation pH value about 8.5, Anaerobic sludge process part is entered by baffle section, after stopping 3.5-4.5h, aerobic treatment unit is entered by discharge outlet.Good In oxygen processing unit, dissolved oxygen 2.5-3.0mg/L is controlled, activated sludge process is used in this experiment, MLSS is 2700-3100mg/ L, after aerobic treatment unit is stopped 4 hours, water outlet enters second pond, after hydraulic detention time is about 2-3h in the second pond, A downflow weir water outlet part is back to anaerobic reation pool, and reflux ratio is 0.5:1-2.0:1, arranged outside remainder, now to waste water Monitoring index is：NH₄ ⁺- N3.1-6.9mg/L, COD40.8-50.5mg/L, pH value 6.83-7.82, reach coking chemistry industry Pollutant emission standard（GB16171-2012）».Because the MAP precipitation method are to waste water NH₄ ⁺- N is pre-processed, then make waste water TN clearances More than 20-30% is improved, processing cost is greatly reduced.

There are three classes to precipitate in the system, a class is the thick slag that Heisui River subsider is produced, outer row is carried out after trench bottom collection Or utilize.Equations of The Second Kind is Ca²⁺The precipitation that reaction settling basin is produced, into precipitation collecting pit, enters heavy by filter feed pump Shallow lake filter, in precipitation filter filtering Hou Song brickmaking, building materials raw material does in factory.Because water quality is more clear after Heisui River subsider precipitation Clear transparent, SS is only 26-40mg/L, so precipitation is with CaCO₃It is main component, white, CaO content is higher than 52% after measured, can Reclaimed as fabulous construction material.3rd class is the precipitation produced in MAP reaction settling basins, PO₄ ^3–In waste water NH₄ ⁺-N、Mg²⁺Ion fully reacts under stirring and alkalescence condition, generation MAP, white precipitate.Due to have passed through removing for early stage Ca²⁺Precipitation, turbidity is less than 20mg/L less than 6NTU, SS content, so precipitation is with MAP as main component, MAP in precipitating after measured Content is higher than 97%, can be reclaimed as the industrial chemicals of high-quality or agricultural slow-release fertilizer, therefore realizes that recycling economy and cleaning are given birth to The theory of product, while also reducing subsequent biochemical processing cost.

The system flow is simple, easily operated, significantly reduces existing A/O system flowbacks ratio, it is ensured that outside biochemical system Effluent NH₄ ⁺- N, TN qualified discharges and stable operation, while rapidly and efficiently reclaiming waste water NH₄ ⁺- N and Ca²⁺、Mg²⁺Resource, realizes The theory of recycling industries and clean production, due to greatly reducing waste water hardness, improves the easy scale problems of water quality, examines equipment Repair cycle stretch-out about more than 6 months.

Application examples two：

With in Zhanjiang section Guangdong refinery Texaco gasifier coal process for making hydrogen produce waste water as objective for implementation, through black Contain Ca in waste water after water subsider precipitation²⁺1009.5-1290.2mg/L、Mg²⁺90-130mg/L、NH₄ ⁺-N272.4- 338.9mg/L, COD787.6-1009.9mg/L, SS are 25-38mg/L, pH value 8.1-8.42, and Heisui River subsider top water outlet is entered Enter Ca²⁺Reaction settling basin, Ca is reached in inflow²⁺After a quarter of reaction settling basin volume, turn on agitator, control turns Speed be 300-350rpm, open plus NaOH pipes to dosing complete, NaOH additions control with Ca in waste water²⁺The mol ratio of ion It is 0.3:1-0.5:1, after being kept stirring for device stirring 15-20min, open plus Na₂CO₃Pipe to dosing is completed, Na₂CO₃Addition control Make with Ca in waste water²⁺The mol ratio of ion is 0.85:1--1.00:1.Go out water dissolves Na with second pond downflow weir₂CO₃、 NaOH, can so save fresh water consumption in technique, while reducing wastewater emission amount.Continue after the completion of water inlet and dosing all Stirring 30min after, adjustment agitator speed be 200-250rpm, and continue stirring 15-20min after, stopping agitator simultaneously stand. After agitator stops and stands 1.5-2h, open and Ca²⁺The connected draining pump of reaction settling basin top discharge outlet, by draining Waste water after pump precipitation is discharged into water leg.Work as Ca²⁺After reaction settling basin racks up waste water, bottom precipitation outlet valve is opened Afterwards, precipitation enters precipitation collecting pit, and precipitation filter is entered by filter feed pump, and brickmaking is sent after precipitation filter filtering Building materials raw material does in factory.

The water outlet of water leg downflow weir enters MAP reaction settling basins by draining pump, and MAP reaction pond bodies are reached in inflow After long-pending a quarter, turn on agitator controls rotating speed for 300-350rpm, opens plus magnesium salts pipe to dosing is completed, addition It is 1.2 to control in the mol ratio with addition microcosmic salt:1--1.5:1, after being kept stirring for device continuation stirring 10-15min, opening phosphorates Salt pipe to dosing complete, addition control with NH in waste water₄ ⁺The mol ratio of-N is 0.6:1—1.1:1, and be kept stirring for, Water inlet and dosing all after the completion of, by pH value detector and plus NaOH manage, regulation reacting solution pH value be not less than 9.0.It is heavy with two Pond downflow weir goes out water dissolves magnesium salts, microcosmic salt, NaOH, can so save fresh water consumption in technique, while reducing discharge of wastewater Total amount.After continuing to stir 10-15min after the completion of water inlet and dosing all, adjustment agitator speed is 150-200rpm, stirring After 20-30min, stop agitator and stand.After 1.5-2h is stood, unlatching is connected with MAP reaction settling basins top discharge outlet Draining pump, the waste water after precipitation is entered by Anaerobic Treatment unit by draining pump.It is to effluent monitoring index now：NH₄ ⁺- N36.1-67.8mg/L, hardness are 45.2-101.3mg/L, COD754.2-982.9mg/L, pH value 8.95-9.93, therefore in warp Cross after precipitation reaction NH in waste water₄ ⁺-N、Ca²⁺、Mg²⁺Ion is significantly removed, and water quality is significantly improved.When MAP reaction precipitations After pond racks up waste water, bottom precipitation outlet valve is opened, precipitation is entered precipitation collecting pit, entered by filter feed pump MAP recovery device.

Waste water after precipitation mixes when entering Anaerobic Treatment unit with the recirculation water from second pond, and pH value of waste water significantly drops It is low, pH8.11-9.17 is generally lowered into, the sour dosage needed for regulation water inlet pH value or need not be so greatly decreased.By adding Acid tube adds hydrochloric acid, and due to the effect of Anaerobic Treatment unit Internal baffle, hydrochloric acid is fully mixed with waste water, after regulation pH value about 8.5, Anaerobic sludge process part is entered by baffle section, after stopping 3.5-4.5h, aerobic treatment unit is entered by discharge outlet.Good In oxygen processing unit, dissolved oxygen 2.5-3.0mg/L is controlled, activated sludge process is used in this experiment, MLSS is 2700-3100mg/ L, after aerobic treatment unit is stopped 4 hours, water outlet enters second pond, after hydraulic detention time is about 2-3h in the second pond, A downflow weir water outlet part is back to anaerobic reation pool, and reflux ratio is 0.5:1-2.0:1, arranged outside remainder, now to waste water Monitoring index is：NH₄ ⁺- N3.1-6.9mg/L, COD40.8-50.5mg/L, pH value 6.83-7.82, reach coking chemistry industry Pollutant emission standard（GB16171-2012）».Because the MAP precipitation method are to waste water NH₄ ⁺- N is pre-processed, then make waste water TN clearances More than 20-30% is improved, processing cost is greatly reduced.

There are three classes to precipitate in the system, a class is the thick slag that Heisui River subsider is produced, outer row is carried out after trench bottom collection Or utilize.Equations of The Second Kind is Ca²⁺The precipitation that reaction settling basin is produced, into precipitation collecting pit, enters heavy by filter feed pump Shallow lake filter, in precipitation filter filtering Hou Song brickmaking, building materials raw material does in factory.Because water quality is more clear after Heisui River subsider precipitation Clear transparent, SS is only 26-40mg/L, so precipitation is with CaCO₃It is main component, white, CaO content is higher than 52% after measured, can Reclaimed as fabulous construction material.3rd class is the precipitation produced in MAP reaction settling basins, PO₄ ^3–In waste water NH₄ ⁺-N、Mg²⁺Ion fully reacts under stirring and alkalescence condition, generation MAP, white precipitate.Due to have passed through removing for early stage Ca²⁺Precipitation, turbidity is less than 20mg/L less than 6NTU, SS content, so precipitation is with MAP as main component, MAP in precipitating after measured Content is higher than 97%, can be reclaimed as the industrial chemicals of high-quality or agricultural slow-release fertilizer, therefore realizes that recycling economy and cleaning are given birth to The theory of product, while also reducing subsequent biochemical processing cost.

The system flow is simple, easily operated, significantly reduces existing A/O system flowbacks ratio, it is ensured that outside biochemical system Effluent NH₄ ⁺- N, TN qualified discharges and stable operation, while rapidly and efficiently reclaiming waste water NH₄ ⁺- N and Ca²⁺、Mg²⁺Resource, realizes The theory of recycling industries and clean production, due to greatly reducing waste water hardness, improves the easy scale problems of water quality, examines equipment Repair cycle stretch-out about more than 6 months.

It is obvious to a person skilled in the art that the utility model is not limited to the details of above-mentioned one exemplary embodiment, and And in the case of without departing substantially from spirit or essential attributes of the present utility model, can in other specific forms realize that this practicality is new Type.Therefore, no matter from the point of view of which point, embodiment all should be regarded as exemplary, and is nonrestrictive, this practicality is new The scope of type limits by appended claims rather than described above, it is intended that the equivalency fallen in claim is contained All changes in justice and scope are included in the utility model.Any reference in claim should not be considered as limitation Involved claim.

Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each implementation method is only wrapped Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should Specification an as entirety, the technical scheme in each embodiment can also be formed into those skilled in the art through appropriately combined May be appreciated other embodiment.

Claims (8)

1. a kind of biochemical treatment system of Texaco stove coal gas wastewater high efficient resourcing, including Heisui River subsider, Ca²⁺Reaction is heavy Shallow lake pond, water leg, MAP reaction settling basins and biological treatment system, it is characterised in that the top delivery port of the Heisui River subsider The import of the first draining pump, the outlet connection Ca of the first draining pump are connected by valve on subsider²⁺The bottom of reaction settling basin Water inlet, Ca²⁺The top delivery port of reaction settling basin connects water leg by the second draining pump, and water leg passes through the 3rd draining pump Connection MAP reaction settling basins, MAP reaction settling basins connect the Anaerobic Treatment list in biological treatment system by the 4th draining pump Unit；Biological treatment system is made up of Anaerobic Treatment unit, aerobic treatment unit and second pond, wherein the draining of Anaerobic Treatment unit Mouth connects aerobic treatment unit by the 5th draining pump, and the top discharge outlet of aerobic treatment unit connects two and sinks by pipeline Pond, and second pond top connects the water inlet of Anaerobic Treatment unit by sewage backflow pipe, second pond bottom passes through sludge reflux Pipe connects Anaerobic Treatment unit and aerobic treatment unit.

2. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, subsider lower valve is installed at the bottom slag discharge of the Heisui River subsider.

3. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the Ca²⁺The bottom of reaction settling basin connects a precipitation collecting pit, a precipitation collecting pit by a mud valve Precipitation filter is connected by filter feed pump.

4. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the bottom of the MAP reaction settling basins connects No. two precipitation collecting pits, No. two precipitation collecting pits by No. two mud valves MAP recovery device is connected by feed pump.

5. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the mud return line connects aerobic treatment unit by a return valve, connected by No. two return valves and detested Oxygen processing unit, mud return line connects the discharge line of second pond by the pipe valve that flows back；Sewage backflow pipe is provided with sewage and returns Stream valve.

6. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the Ca²⁺An agitator and No. two agitators are respectively equipped with reaction settling basin and MAP reaction settling basins.

7. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the Ca²⁺Reaction settling basin top is set plus NaOH pipes and plus Na₂CO₃Pipe, MAP reaction settling basins top sets and adds Magnesium salts pipe, the salt pipe that phosphorates, plus NaOH pipe and a pH value detector；The water inlet of Anaerobic Treatment unit sets acid adding pipe, top It is provided with No. two pH detectors.

8. the biochemical treatment system of a kind of Texaco stove coal gas wastewater high efficient resourcing according to claim 1, it is special Levy and be, the Anaerobic Treatment unit inlet end pond it is long 1/5th at core wall is set, by Anaerobic Treatment unit point Into two ponds, several baffle plates are being set in the pond of inlet end.